Peroxygen bleach activators and bleaching compositions

ABSTRACT

This invention relates to peroxygen bleaching activator compounds and bleaching compositions. The peroxygen bleach activator compounds, used in combination with peroxygen bleach compounds which yield hydrogen peroxide in an aqueous solution, provide effective and efficient bleaching of textiles over a wide range of temperatures. In a highly preferred embodiment the bleaching compositions of the invention are detergent compositions.

REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent applicationSer. No. 564,786 filed Dec. 22, 1983, now U.S. Pat. No. 4,483,778.

TECHNICAL FIELD

This invention relates to novel compounds and compositions useful inperoxygen bleaching. More particularly, this invention relates to novelperoxygen bleach activator compounds that aid in providing effective andefficient peroxygen bleaching of textiles over a wide range oftemperatures and conditions.

This invention also relates to bleaching detergent compositionsemploying these peroxygen bleach activator compounds in combination witha peroxygen bleaching compound capable of yielding hydrogen peroxide insolution. In a highly preferred embodiment the bleaching compositions ofthe present invention are stable detergent compositions. This inventionfurther relates to methods of making the peroxygen bleach activatorcompounds. Lastly, this invention relates to particularly stable bodiescontaining these peroxygen bleach activator compounds in combinationwith certain binder or enrobing compounds.

It is well known that peroxygen bleaches are effective in removingstains and/or soils, as well as visible evidence of stains and/or soils,from textiles. Unlike sodium hypochlorite bleaching solutions, they canbe readily employed in a variety of bleaching and detergentcompositions. However, the efficacy of peroxygen bleaches can varygreatly with temperature. These bleaches are only practicable and/oreffective when the bleaching solution (bleach and water mixture) isabove about 60° C. When employed in a bleach solution at a temperatureof about 60° C. for below, peroxygen bleaches are significantly lessefficacious than at higher temperatures. Therefore, in order to obtain adesirable level of bleaching performance at these lower temperatures,extremely high levels of peroxygen bleach must be employed. Due to thecost of peroxygen bleach compounds, levels necessary to achieve goodbleaching performance at such temperatures are economicallyimpracticable. In bleach solutions where the temperature is well below60° C., peroxygen bleaches are rendered almost totally ineffectiveregardless of the level of peroxygen bleach compound added to thesystem.

The dependence of peroxygen bleach performance on temperature (andconcentration), described above, is both practically and economicallysignificant. Peroxygen bleaches are most commonly used as detergentadjuvants in home laundry products. Thus, the typical textile washprocess employing these bleaches utilizes as automatic household washingmachine and a wash-water temperature below 60° C. (The low wash-watertemperature utilized reflects concern for both textile care and energyconsumption.) As a consequence, there has been much interest indeveloping substances that would increase the efficacy of peroxygenbleach compounds allowing them to be effectively employed at atemperature below 60° C. Such substances are generally referred to inthe art as bleach activators or peroxygen bleach activators.

BACKGROUND OF THE INVENTION

Numerous substances have been disclosed in the art as effectiveperoxygen bleach activators. Among the best known of these are thesubstituted and unsubstituted carboxylic acid ester bleach activators.

U.S. Pat. No. 3,130,165, Brocklehurst, issued Apr. 21, 1964, describes ahousehold laundry detergent composition. This composition contains adetergent, from 3-20% by weight of an inorganic peroxy-compound, andfrom about 0.5 to about 2.5 moles of a phenol (or substituted phenol)ester of alpha-chloro-acetic or -propionic acid per mole of availableoxygen.

Detergent Age, July, 1967, describes chloroacetyl salicylic acid as anactivator for low temperature perborate/peroxide bleaching.

U.S. Pat. No. 3,075,921, Brocklehurst, et al., issued Jan. 29, 1963,discloses 2-chloro, 4-chloro, and 2-methoxy peroxybenzoic acid. Theseacids are described as providing excellent bleaching activity whenincorporated into solid detergent compositions.

British Patent Specification No. 864,798, published Apr. 6, 1961,discloses bleaching compositions comprising an inorganic persaltcombined with an organic ester of an aliphatic carboxylic acid. Theaddition of these esters to the wash solution is said to give a morevigorous bleaching action than the hydrogen peroxide alone. Such asystem therefore permits low-temperature bleaching (50°-60° C.) underotherwise normal washing conditions. It is preferred that the ester bederived from an aliphatic aliphatic carboxylic acid having not more than10, and preferably less than 8, carbon atoms. The patentee states thatsuch bleaching compositions are stable during storage.

British Patent Specification No. 836,988, published June 9, 1960,describes bleaching and detergent compositions containing an inorganicpersalt and an organic carboxylic acid ester. It is alleged that suchesters provide improved bleaching at temperatures between 50° to 60° C.when compared to systems employing the persalt alone. Specific examplesinclude sodium dodecyl benzene sulfonate and sodium dodecyl phenylacetate.

It is also known that bleach activators which exhibit surface activitycan be used in combination with peroxygen-type bleaches to provideparticularly effective surface bleaching. U.S. Pat. No. 4,283,301,Diehl, issued Aug. 11, 1981, discloses bleaching compositions comprisinga peroxygen bleach, such as persalt, and a bleach activator. Theactivators described are esters of either an alkyl mono- ordi-carboxylic acid. These activators may be represented by the generalformula: ##STR1## wherein R is an alkyl chain containing from about 5 toabout 13 carbon atoms, R² is an alkyl chain containing from about 4 toabout 24 carbon atoms, and Z is a leaving group. The patentee statesthat the selected bleach and bleach activator are preferably present inequimolar ratios.

U.S. Pat. No. 4,412,934, Chung, et al., discloses bleaching compositionscontaining a peroxygen bleaching compound and a bleach activator of thegeneral formula: ##STR2## wherein R is an alkyl group containing fromabout 5 to about 18 carbon atoms with the longest linear alkyl chainbeing from about 6 to about 10 carbon atoms; L is a leaving group. It isfurther required that the conjugate acid of the activator must have apK_(a) in the range of from about 6 to about 30. The molar ratio of thehydrogen peroxide generated:activator must be greater than about 1.5:1.

Certain benzene sulphonate compounds with an alkoxy group substituted onthe ring are known to be useful in cleaning compositions. U.S. Pat. No.3,685,127, Boldingh, et al., issued Aug. 22, 1972, describes detergentcompositions with improved bleaching capability containing (1) aninorganic persalt, (2) an organic detergent and (3) a bleach precursorhaving the general formula: ##STR3## wherein X is a branched or straightchain alkyl or alkanoyl radical containing 6 to 17 carbon atoms, R ishydrogen or an alkyl radical having 1 to 7 carbon atoms, and M is analkali metal or ammonium radical. Spray-dried detergent compositionscontaining 2-acetoxy-5-nonyl benzene sulfonate are disclosed.

Certain alpha-chloro and alpha-alkoxy acid esters are known to be usefulas perfumes in cleaning compositions. For example, U.S. Pat. No.3,368,943, Gilbert, issued Feb. 13, 1968, discloses compounds of theformula: ##STR4## wherein a is 0 or 1; X is chlorine or bromine; R ismethyl or ethyl; and R' is a saturated C₄ -C₁₂ aliphatic branched orlinear chain, benzyl, phenol ethyl, or phenol propyl radical. Thecompounds described by the patentee are said to possess an agreeableodor. These compounds include alpha-alkoxy isobutyrates and alpha-halobeta-alkoxy isovalerates. As perfumes, these compounds are said to beparticularly suitable for use in detergents and "bleaching-aid"compositions. Cleaning compositions, detergent compositions, and barsoap compositions perfumed with these compounds are disclosed.

Poly-alpha-chloro acrylic acid is disclosed in the art as being usefulin detergent compositions as both an oxidizing agent and as a thickener.British Patent Specification No. 1,420,468, published Jan. 7, 1976,suggests that oxidizing agents can be generated in a wash solution ifthe original detergent compositions contain a combination of sodiumperborate and a poly-alpha-hydroxy acrylic acid, a poly-alpha-chloroacrylic acid, or a derivative of these compounds.

U.S. Pat. No. 3,553,140, McCrudden, issued May 15, 1979, disclosescertain carboxyl-group-containing polymers useful as thickeners indetergent compositions which additionally contain a perborate.Alpha-chloro acrylic acid in a detergent composition is specificallydisclosed.

U.S. Pat. No. 3,969,257, Murray, issued July 13, 1976, suggests thatacetyl salicylic acid is useful as an activator for soluble peroxidebleaching agents in detergent compositions.

While the overall efficacy of carboxylic acid ester bleach activatorsmost similar to those of the present invention is unquestioned, theseart-disclosed compounds most similar to those of the present inventionsuffer from one significant drawback: they yield compounds (the activecomponent) which possess a particularly repugnant odor under actualusage conditions (pH, temperature, etc.). Because they possess this odorunder actual wash conditions, their overall utility and value is greatlyreduced.

The malodor associated with these compounds (the active component) iswell-known in the art. See "Organic Peroxides and Peroxy Compounds",Kirk-Othmer Encyclopedia of Chemical Technology, 17,60.

U.S. Pat. No. 4,009,113, Green, et al., issued Feb. 22, 1977, disclosesgranular compositions comprising from about 40% to about 80% of a bleachactivator and an inert carrier material such as long chain fatty acidsor esters wherein said precursor is substantially evenly distributedwith said precursor compound to form a composite particle. The particlehas an outer protective layer which can consist of, for example,polyvinyl alcohol. It is stated that such compositions have both goodstorage stability and dispersibility in the wash water.

U.S. patent application Ser. No. 362,812, Gray, et al., filed Mar. 29,1982, discloses a detergent additive composition comprising from about75% to about 95% of a particulate infusible solid having a particle sizedistribution such that at least about 50% thereof passes a 250micrometer screen and comprising storage sensitive detergent additivematerials, and from about 5% to about 25% of ethoxylated nonionicsurfactants melting in the range of from about 20° C. to about 60° C.wherein said composition is prepared via a radial extrusion process. Itis stated that such compositions have improved storage stabilitytogether with excellent release and dispersibility characteristics inwash water.

U.S. patent application Ser. No. 433,499, Chung, filed Oct. 8, 1982,"Bodies Containing Bleach Activator", describes stable compositionsemploying binder and enrobing materials similar to those of the presentinvention. These compositions contain 4-(alkanoyloxo)benzenesulfonates.

It has now been discovered that certain alpha substituted derivatives ofthe C₆ -C₁₈ carboxylic acid esters provide particularly effectiveperoxygen surface bleaching performance but do so without generating themalodor associated with the use of corresponding unsubstituted orshorter chain (art-disclosed) compounds.

It has also been discovered that these alpha substituted C₆ -C₁₈carboxylic acid esters, while very reactive, can be stabilized forstorage by forming bodies containing the esters and select binder orenrobing materials, such as sorbitan esters.

It has further been discovered that these alpha substituted C₆ -C₁₈carboxylic acid esters can be simply prepared under anhydrous conditionswithout generating noxious products.

SUMMARY OF THE INVENTION

The present invention comprises peroxygen bleach activator compounds ofthe general formula ##STR5## wherein R is a straight or branched alkylor alkenyl group having from about 4 to about 14 carbon atoms, R¹ is H,CH₃, C₂ H₅, or C₃ H₇, X' is Cl, OCH₃, or OC₂ H₅, and L is a leavinggroup as defined herein. The present invention also comprises bleachingand detergent compositions containing compounds of the general formuladescribed above and a peroxygen bleaching compound capable of yieldinghydrogen peroxide in an aqueous solution wherein the ratio of peroxygenbleaching compound to peroxygen bleach activator compound is about 10:1to about 1:4.

This invention also comprises a method of making the alpha-substitutedalkyl or alkenyl compounds above, where L is an oxybenzene sulfonate,comprising reacting the corresponding substituted acid chloride with thedisodium salt of L under anhydrous conditions.

Further, the present invention comprises a body containing bleachactivators comprising:

(a) from about 50% to about 98% of a bleach activator compound of thegeneral formula ##STR6## where R is a straight or branched alkyl oralkenyl group having from about 4 to about 14 carbon atoms, R¹ is H orC₂ H₅, X is Cl, OCH₃ or OC₂ H₅ and L is a leaving group selected from##STR7## wherein R² is an alkyl chain containing from about 1 to about 8carbon atoms, and Y is --SO₃ ⁻ M⁺ or COO⁻ M⁺ wherein M⁺ is sodium orpotassium; and

(b) from about 2% to about 50% of a binder material selected from thegroup consisting of nonionic surfactants, polyethylene glycols, anionicsurfactants, film forming polymers, fatty acids and mixtures thereof,wherein said binder does not melt below about 40° C.; and wherein (a)and (b) are substantially evenly distributed throughout said body, thedensity of said body is above about 1.06 g/cc and said body containsless than about 5% water. Preferred binder or enrobing materials includesorbitan monopalmitate, sorbitan monostearate, sorbitan distearate,sorbitan tristearate, or mixtures of these compounds.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to novel alpha substituted alkyl or alkenylesters useful as peroxygen bleach activators. These activators, whenused in combination with a peroxygen bleach compound capable of yieldinghydrogen peroxide in an aqueous solution, at specific molar ratios ofavailable hydrogen peroxide in solution to activator, provide extremelyeffective and efficient bleaching of stains from textiles. Suchcompositions remove stains and/or soils from textiles, as well as thevisible evidence of stains and/or soils. The bleaching activity of thesecompositions makes them particularly effective in the removal of dingysoils. Dingy soils are frequently a blend of particulate and greasymaterials that build up on textiles after numerous washings; these soilsgive white textiles a gray tint. Removing soils of this type issometimes referred to in the art as "dingy fabric clean-up".

The bleaching compositions employing the activators of the presentinvention provide this effective bleaching over a wide range oftemperatures. Without the bleach activator compounds of the presentinvention, such peroxygen bleaching compounds would be ineffectiveand/or impractical at temperatures below about 60° C. The improvedbleaching activity obtained by employing the activators of the presentinvention is observed when the bleach solution temperature is at leastabout 5° C.

Compounds similar to those of the present invention which are known inthe art can be logically separated into two classes. The first class ofknown compounds are the corresponding unsubstituted compounds, compoundswith similar or identical chain lengths and leaving groups but withoutthe chlorine, methoxy or ethoxy group substituted at the alpha (2)position. The second class of known compounds are compounds with thechlorine, methoxy or ethoxy substitution but possessing a chain length(the alkyl or alkenyl chain with the substitution) of only 2-3 carbonatoms. The activators most similar to those of the instant inventionfrom both of these clases of compounds suffer from the samedisadvantage: they yield compounds (the active component or species)which possess an offensive, unpleasant odor under actual usageconditions (pH, temperature, etc.). This characteristic malodor makesthe use of either class of known compounds undesirable for two reasons.First, this odor is detectable when the compounds are placed insolution, i.e. during use. Second, the malodor associated with thesecompounds lingers, remaining on any textile or fabric which has beenplaced in a bleaching solution containing them. Thus, the malodor isnoticeable both during and after use.

The compounds of the present invention, particularly the alpha chlorosubstituted compounds, possess two significant advantages over theart-disclosed compounds discussed above. Most importantly, they do notgenerate, either during or after use, the malodor which ischaracteristic of the use of the art-disclosed compounds. Secondly,under common usage conditions, the compounds of the present inventionare frequently capable of providing equivalent peroxygen bleaching whileemploying lower levels of peroxygen bleaching compound than would berequired for the art-disclosed compounds. In this context they are moreefficient.

Peroxygen Bleach Activators

The present invention comprises peroxygen bleach activator compounds ofthe general formula ##STR8## wherein R is a branched or linear alkyl oralkenyl group having from about 4 to about 14 carbon atoms; R¹ is H,CH₃, C₂ H₅ or C₃ H₇ ; X' is Cl, OCH₃ or OC₂ H₅ ; and L is a leavinggroup the conjugate acid of which has a pK_(a) in the range of fromabout 4 to about 30. These compounds, when used in combination with aperoxygen bleaching compound capable of yielding hydrogen peroxide in anaqueous solution, provide particularly effective peroxygen bleachingover a wide range of temperatures and conditions.

L in the above formula can be essentially any useful leaving group. Aleaving group is any group that is displaced from the bleach activatorin a peroxygen bleaching solution as a consequence of the nucleophilicattack on the bleach activator by the perhydroxide anion. Thisperhydrolysis reaction results in the formation of a percarboxylic acid.Generally, for any group to be useful as a leaving group in thecompounds and compositions of the present invention, it must exert anelectron attraction or an "electron attracting effect". This facilitatesthe formation of the peroxy acid anion. Leaving groups that exhibit thisbehavior are those with a corresponding conjugate acid that has a pK_(a)in the range of from about 4 to about 30, preferably about 4 to 16, morepreferably about 6 to about 13, and even more preferably from about 7 toabout 11. If sustained bleaching activity over a long period of time isdesired, then employing groups with pK_(a) values other than thoseindicated as preferred (different perhydrolysis rates), or mixtures ofgroups having various pK_(a) values, may be desirable.

Preferred bleach activator compounds of the present invention are thoseof the above general formula (I) wherein R, R¹ and X' are as defined inthe general formula (I) and L is selected from the group consisting of:##STR9## wherein R² is an alkyl chain containing from about 1 to about 8carbon atoms, R³ is H or an alkyl chain containing from about 1 to about8 carbon atoms, and Y is H or a group which provides solubility (asdefined herein) to the bleach activator compounds of the presentinvention in water at 5° C. or 45° C., hereinafter referred to as "asolubilizing group". The preferred solubilizing groups are --SO₃ ⁻ M⁺,--COO⁻ M⁺, -SO₄ ⁻ M⁺, (--N⁺ R₃ ⁴)X⁻ and O←NR₂ ⁴, and most preferably--SO₃ ⁻ M⁺ and --COO⁻ M⁺, wherein R⁴ is an alkyl chain containing fromabout 1 to about 4 carbon atoms, M is a cation which, when combined withX, provides solubility to the bleach activator compounds of the presentinvention. Preferably, M is an alkali metal, ammonium or substitutedammonium cation, with sodium and potassium being most preferred, and Xis a halide, hydroxide, methylsulfate or acetate anion. It should benoted that bleach activator compounds of the present invention whichpossess a leaving group that does not contain a solubilizing groupshould be well dispersed when employed in a bleaching solution in orderto assist in their dissolution. By providing solubility, as used herein,is meant that the group or groups selected make the final bleachactivator compound sufficiently soluble to provide a concentration atleast 3 parts per million of activator in the bleach solution at either5° C. or 45° C., or at both temperatures.

Alpha substituted (Cl, or OCH₃ or OC₂ H₅) alkyl or alkenyl carboxylicacid diol, polyol, and sugar esters are also useful. Preferred sugarester bleach activator compounds of the present invention includeglucose, sucrose, and lactose esters of the formula ##STR10## wherein Ais H or ##STR11## wherein R is a branched or linear alkyl or alkenylgroup having from about 4 to about 14 carbon atoms; R¹ is H, CH₃, C₂ H₅or C₃ H₇ ; and X' is Cl, OCH₃ or OC₂ H₅ ; provided that at least one Ais not H. In preferred sugar ester peroxygen bleach activator compoundsof the present invention, no A is H.

Preferred bleach activator compounds of the present invention are alsothose of the above general formula (I) wherein L, X' and R¹ are asdefined in the general formula (I) and R is a branched or linear, andpreferably linear, alkyl group containing from about 4 to about 10carbon atoms. Those having a linear alkyl R group containing from about6 to about 10 are more preferred. Even more preferred are bleachactivator compounds of the present invention of the above generalformula (I) wherein L is as defined in the general formula and R is alinear alkyl chain containing from about 6 to about 8 carbon atoms.

Preferred bleach activator compounds of the present invention are thoseof the above general formula (I) wherein R and L are as defined above,and R¹ is H or C₂ H₅, with R¹ as H particularly preferred.

Thus, the preferred bleach activator compounds of the present inventionare those of the above general formula (I) wherein R is a linear alkylchain containing from about 6 to about 10, and more preferably fromabout 6 to about 8 carbon atoms, R¹ is H or C₂ H₅, and preferably H, X'is Cl, and L is selected from the group consisting of: ##STR12## whereinR, R², R³ and Y are as defined above.

More preferably, the bleach activator compounds of the present inventionare those of the above general formula (I) wherein R is a linear alkylgroup containing from about 6 to about 10 carbon atoms, X' is Cl, R¹ isH or C₂ H₅, preferably H, and L is selected from the group consistingof: ##STR13## wherein R² is as defined above and Y is --SO₃ ⁻ M⁺ or--COO⁻ M⁺ wherein M is as defined above.

Preferred branched akyl chain bleach activator compounds of the presentinvention are those of the above general formula (I) wherein R is abranched alkyl chain containing from about 6 to about 12 carbon atomswherein the longest linear alkyl portion of said chain contains fromabout 4 to about 10 carbon atoms, X' is Cl, R¹ is H or C₂ H₅, and L isselected from the group consisting of ##STR14## wherein R² is an alkylchain containing from about 1 to about 8 carbon atoms, Y is --SO₃ ⁻ M⁺or --COO⁻ M⁺ wherein M is sodium or potassium

Highly preferred bleach activator compounds of the present invention arethose of the above general formula (I) wherein R is a linear alkyl chaincontaining from about 6 to about 10, and preferably from about 6 toabout 8 carbon atoms, R¹ is H or C₂ H₅, and preferably H, X is Cl and Lis selected from the group consisting of: ##STR15## wherein R² is asdefined above and Y is --SO₃ ⁻ M⁺ or --COO⁻ M⁺ wherein M is as definedabove.

The most highly preferred bleach activator compounds of the presentinvention are of the formula: ##STR16## wherein R is a linear alkylchain containing from about 6 to about 10, and preferably from about 6to about 8, carbon atoms, and M is sodium or potassium.

Representative peroxygen bleach activator compounds of the presentinvention include, without limitation, ##STR17## Sodium4-(2-chlorooctanoyloxy)benzenesulfonate; ##STR18## Sodium4-(2-chlorononanoyloxy)benzenesulfonate; ##STR19## Sodium4-(2-chlorodecanoyloxy)benzenesulfonate; ##STR20## Sodium4-(3,5,5-trimethyl-2-chlorohexanoyloxy)benzene sulfonate; ##STR21##Sodium 4-(2-chloro-2-ethyl-hexanoyloxy)benzenesulfonate; ##STR22##Sodium 2-(2-chlorooctanoyloxy)benzenesulfonate ##STR23## Sodium2-(2-chlorononanoyloxy)benzene sulfonate ##STR24## Sodium2-(2-chlorooctanoyloxy)benzoate ##STR25## Sodium2-(2-chlorononanoyloxy)benzoate ##STR26## Sodium4-(2-chlorooctanoyloxy)benzoate and ##STR27## Sodium4-(2-chlorononanoyloxy)benzoate

THE PEROXYGEN BLEACHING COMPOSITION

The present invention also comprises bleaching and detergentcompositions containing compounds of the general formula (I) describedabove and a peroxygen bleach compound capable of yielding hydrogenperoxide in an aqueous solution wherein the ratio of peroxygen bleachcompound to peroxygen bleach activator compound is about 10:1 to about1:4, by weight of the composition. Ratios of about 3:1 to about 1:2 arepreferred, with ratios of about 3:1 to about 1:1, by weight of thecomposition, particularly preferred.

The preferred molar ratio of available hydrogen peroxide generated insolution (the bleaching solution or liquor) by the peroxygen bleachcompound to bleach activator compound is about 3:1 to about 1:3. Itshould be noted that such a ratio can also generally be expressed as themolar ratio of peroxygen bleach compound to peroxygen bleach activatorbecause the vast majority of peroxygen bleach compounds theoreticallyyield one mole of hydrogen peroxide (in solution) per mole of peroxygenbleach compound.

It will be appreciated by examining the preferred ratios (of peroxygenbleach compound to peroxygen bleach activator compound) described above,that the bleaching compositions of the present invention possess asecond significant advantage over many very similar art-disclosedcompounds; they are extremely efficient. Much lower levels of theperoxygen bleach activator compounds of the present invention arerequired (on a molar basis) to achieve bleaching performance equivalentto that of many very similar art-disclosed compounds.

The peroxygen bleach activators of the present invention areparticularly useful in peroxygen bleaching compositions designed for thesurface bleaching of fabrics or textiles, especially dingy soilclean-up. The peroxygen bleaching compounds useful herein, i.e., incombination with one or more of the peroxygen bleach activators of thepresent invention, are those capable of yielding hydrogen peroxide in anaqueous solution. These compounds are well known in the art and includehydrogen peroxide; the alkali metal peroxides; organic peroxidebleaching compounds such as urea peroxide; and inorganic persaltbleaching compounds, such as the alkali metal perborates, percarbonates,perphosphates, and the like. Mixtures of two or more such bleachingcompounds, or mixtures of two or more activator compounds, can also beused, if desired.

Preferred peroxygen bleach activator compounds of the present inventionfor use in bleaching compositions include sodium4-(2-chlorooctanoyloxy)benzenesulfonate; sodium4-(2-chlorononanoyloxy)benzenesulfonate; sodium4-(2-chlorodecanoyloxy)benzenesulfonate; sodium4-(3,5,5-trimethyl-2-chlorohexanoyloxy)benzenesulfonate; sodium4-(2-chloro-2-ethylhexanoyloxy)benzenesulfonate; sodium2-(2-chlorooctanoyloxy)benzenesulfonate; sodium2-(2-chlorononanoyloxy)benzenesulfonate; and sodium2-(2-chlorodecanoyloxy)benzenesulfonate; sodium4-(2-chlorononanoyloxy)benzenesulfonate; sodium4-(2-chlorodecanoyloxy)benzenesulfonate; and sodium4-(2-chlorodecanoyloxy)benzenesulfonate.

Preferred peroxygen bleaching compounds include sodium perborate,commercially available in the form of mono- and tetrahydrates, sodiumcarbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, and sodium peroxide. More preferably, the peroxygenbleaching compound is selected from the group consisting of sodiumperborate monohydrate, sodium perborate tetrahydrate, and sodiumcarbonate peroxyhydrate. Particularly preferred are sodium perboratetetrahydrate and sodium perborate monohydrate. Sodium perboratemonohydrate is especially preferred because it is stable during storageyet dissolves very quickly in the bleaching solution. It is believedthat such rapid dissolution results in the formation of higher levels ofpercarboxylic acid and, thus, enhances surface bleaching performance.

Useful levels of peroxygen bleach compound within the bleachingcompositions of the invention are from about 0.1% to about 95%, andpreferably from about 1% to about 60%, by weight of the bleachingcomposition, preferably utilizing the ratios described above. When thebleaching compositions within the invention are also detergentcompositions it is preferred that the level of peroxygen bleach is fromabout 1% to about 20%, by weight of the detergent composition,preferably utilizing the peroxygen bleach compound:peroxygen bleachactivator weight ratios described above.

The level of bleach activator compound within the compositions of theinvention is from about 0.1% to about 60%, and preferably from about0.5% to about 40%, more preferably about 0.5% to about 20%, by weight ofthe bleaching composition, preferably utilizing the peroxygen bleachcompound:peroxygen bleach activator weight ratios described above. Whenthe bleaching compositions within the invention are also detergentcompositions it is preferred that the level of bleach activator is fromabout 0.5% to about 20%, and more preferably about 5% to about 20% byweight of the detergent composition, preferably utilizing the peroxygenbleach compound:peroxygen bleach activator weight ratios describedabove.

In a particularly preferred embodiment of the present invention thebleach activator compounds are employed in a mixture with otherconventional peroxygen bleach activators. For example, mixtures of thecompounds of the present invention in the peroxygen bleach activatorsdescribed in U.S. Pat. No. 3,130,165 (Brocklehurst) issued Apr. 21,1964; British Patent Specification No. 864,798, published Apr. 6, 1961;British Patent Specification No. 836,988, published June 9, 1960; U.S.Pat. No. 4,283,301 (Diehl) issued Aug. 11, 1981; U.S. Pat. No. 3,075,921(Brocklehurst et al) issued Jan. 29, 1963; U.S. Pat. No. 4,412,934(Chung et al) issued Nov. 1, 1983; and U.S. Pat. No. 3,936,537(Baskerville et al) issued Feb. 3, 1976, all incorporated herein byreference may be employed. Preferred peroxygen bleach activators for usein combination with the compounds of the present invention in thebleaching compositions of the present invention include sodium4-octanoyloxybenzene sulfonate, sodium 4-nonanoyloxybenzenesulfonate,sodium 4-decanoyloxybenzene sulfonate, tetra acetyl ethylene diamine,tetra acetyl methylene diamine, and tetra acetyl glycouril. Especiallypreferred peroxygen bleach activators are sodium4-nonanoyloxybenzenesulfonate, sodium 4-octanoyloxybenzenesulfonate andsodium 4-decanoyloxybenzene sulfonate. The level of conventionalactivators to the activator of the present invention is from about 10%to about 90%, preferably from about 30% to about 70%, more preferablyfrom about 40% to about 60% by weight of the total activator. A highlydesirable mixture comprises the substituted activators of this inventionand the corresponding unsubstituted activators. Such a mixture canresult from using a mixture of acyl groups resulting from the method ofmanufacture. Especially preferred combinations are those in which theacyl groups have carbon chain lengths from about C₈ to about C₁₀.

The mixtures described above deliver several unexpected benefits. Thecombination of substituted activators and unsubstituted activatorsexhibits a preferred odor profile under the soil conditions of thetypical wash load as compared to the individual activators. Thecombination of the alpha-chloro substituted activators and the linearunsubstituted activator exhibit very good odors under typical soilloading conditions. Further, mixtures show no significant loss inbleaching effectiveness from the 100% linear unsubstituted activator asshown herein. Further, mixtures allow a decrease in the amount ofperborate in a detergent composition without a resulting decrease inbleaching effectiveness. Finally, the combinations offer improvedsolubility, improved low temperature bleaching, and a cost savingsbenefit. By using the mixtures, a lower purity of the alphachlorinatedactivator is acceptable and even desirable. This greatly reduces thecost involved in making the activator compounds herein.

The bleaching compositions of the present invention, including detergentcompositions, are preferably employed at a pH (i.e., bleaching ordetergent solution or liquor) of about 8 to about 11, with a pH of about8.5 to about 10.5 preferred.

BLEACH BODIES

The character of peroxygen bleach activator compounds can besignificantly altered during storage. (See U.S. Pat. No. 4,412,934,Chung, et. al., issued Nov. 1, 1983.) This is particularly true of thebleach activator compounds of the present invention. If stored as partof a bleaching or detergent composition, the peroxygen bleach activatorsof the present invention may interact with other bleaching (e.g.,perborate) or detergent components. They may also react with themoisture inherently present in either type of composition, or with themoisture in the environment in which they are stored. The bleachactivator compounds of the present invention must therefore be protectedfrom the environment during storage to retain efficacy. However, it iscritical that the selected method of protecting the bleach activatorcompounds of the present invention from their environment (especiallymoisture) during storage not substantially inhibit their ability todisperse in water.

This invention relates to a body containing stabilized, particulateperoxygen bleach activators which comprises specific bleach activatorsand binder or enrobing materials, both of which are defined herein. Theperoxygen bleach activators incorporated in the body have excellentstorage stability (are well protected from their environment) and yetreadily disperse and release in water. Also, when the bodies are formedin the practice of the present invention, a superior level of bleachingperformance on textiles is obtained.

It is preferred that the peroxygen bleach activator and binder orenrobing material are substantially evenly distributed throughout thebody. The body must also have the proper density. Compacting the bleachactivator compound particles to form a body with a density within theinvention and then coating it with the binder material may not providethe maximum level of storage stability. Only when the bleach activatorand binder material are substantially evenly distributed throughout thebody is the storage stability maximized. However, it is also essentialthat the density of the body be above about 1.06 grams/cubic centimeter(g/cc), preferably above about 1.08 g/cc, most preferably from about1.10 g/cc to about 1.30 g/cc. When the peroxygen bleach activator andbinder or enrobing material are substantially evenly distributedthroughout the body, densities below about 1.06 g/cc may not provide thedesired level of storage stability.

Specific densities may be measured by a mercury displacement method,described as follows. Air is removed from a vessel containing a weighedsample of the particles (bodies), mercury is introduced, and thepressure increased in increments. The rate of volume decrease (ordensity increase) is typically one value when interparticulate spacesare being filled, which occurs first, and a different value when thevoids in the particle are being filled. The inflection point on thevolume-pressure curve is taken as indicating the specific density of theparticles.

To achieve maximum storage stability, the body should also beessentially free of moisture. The presence of excess free moisture willresult in very poor storage stability because of the peroxygen bleachactivator's susceptability to hydrolysis. Thus, preferred bodies containless than about 5% water, more preferably less than 3% water, and mostpreferably less than about 1.5% water, by weight of the body.

Control of the particle size of the body is also of some importance forobtaining optimum storage stability and dispersibility in the washwater. It is preferred that the bodies of the present invention, whenemployed in a bleaching or detergent composition, have a particle sizedistribution of from about 50 microns to about 2.5 millimeters whereinno more than about 5% of the bodies are greater than about 2millimeters. More preferably, the bodies of the present invention, whenemployed in a bleaching or detergent composition, have a particle sizedistribution of from about 300 microns to about 1.5 millimeters.

The body can be made by essentially any apparatus that is suitable tosubstantially evenly distribute the bleach activator and binder materialthroughout the body and compact the body in order to obtain the requireddensity. For example, powder blenders can be utilized to mix the bleachactivator and binder material and then the mixture can be passed througha radial or axial extruder. A compaction press may also be employed toform the body. Radial or axial extruders are preferred because it isbelieved that they produce a body in which the bleach activator has bothsuperior storage stability and dispersibility in the wash water. Whenthe bleach activator and binder material are mixed, the binder materialis preferably in fluid form. This can be accomplished by heating themixture until the binder material melts. When employing binder materialsthat decompose rather than melt upon heating, an aqueous solution can beformed.

The following is a detailed description of the essential components ofthe body containing the peroxygen bleach activators of the presentinvention. All percentages, parts and ratios are by weight of the bodyunless otherwise indicated.

The level of bleach activator useful within the bodies of the presentinvention is from about 50% to about 99.5%, preferably about 50% toabout 98%, and more preferably from about 85% to about 96%, by weight ofthe body.

Bleaching compositions employing the bodies of the present inventioncomprise from about 0.1% to about 60%, and preferably about 0.5% toabout 40%, by weight of the composition of the bodies of the presentinvention, and from about 0.1% to about 95%, preferably about 1% toabout 60%, by weight of the composition, of a peroxygen bleachingcompound capable of yielding hydrogen peroxide in an aqueous solution.When these bleaching compositions are also detergent compositions, it ispreferred that the level of bleach bodies is from about 0.5% to about20%, by weight of the detergent composition, and that the level ofperoxygen bleaching compound is from about 1% to about 20%, by weight ofthe detergent composition, and that the composition further comprisesabout 1% to about 30% of a detergent surfactant. Preferred ratios ofbodies:peroxygen bleaching compound are the same as those describedherein for activator alone to peroxygen bleaching compound.

It is also preferred that the bleach activator particle sizedistribution within the bleaching or detergent composition is from about5 microns to about 2.5 millimeters. More preferably, no more than about2% of the particles are greater than about 2 millimeters. Mostpreferably, the particle size distribution is from about 25 microns toabout 150 microns.

THE BINDER OR ENROBING MATERIALS

The materials that can be utilized as binders or enrobing materials arethe nonionic surfactants, polyethylene glycols, fatty acids, anionicsurfactants, film forming polymers and mixtures of these materials. Itis believed that such binder or enrobing materials are not reactive withthe bleach activators of the present invention. If the body is placed ina detergent composition, the binder or enrobing material should not bereactive with the components of the detergent composition upon storage.Ideal binder or enrobing materials have a low hygroscopicity uponstorage but should be soluble or dispersable in water. This allows fordispersion and release of the peroxygen bleach activator in the bleachor wash solution. It is also essential that the employed binder orenrobing materials do not melt below about 40° C. The binder wouldlikely melt upon storage; frequently the storage temperature for suchcompositions is as high as 40° C. Any melting of the binder or enrobingmaterial results in the bleach activator being quite unstable. (Whilesome of the binder materials within the invention will decompose ratherthan melt upon exposure to of heat, the temperature at which such bindermaterials decompose is well beyond any temperature at which the bodieswill likely be stored.)

Examples of other nonionic surfactants that can be utilized as binder orenrobing materials are the condensation products of primary or seconaryaliphatic alcohols having from 8 to 24, and preferably about 9 to about18, carbon atoms, in either a straight or branched chain configuration,with from about 35 to about 100 moles, and preferably about 40 to about80 moles, of ethylene oxide per mole of alcohol. The preferred nonionicsurfactants are prepared from primary alcohols which possess eitherlinear (such as those derived from natural fats, or prepared by theZiegler process from ethylene, e.g., myristyl, cetyl, and stearylalcohols), or partly branched carbon chains (such as the Dobanols andNeodols which have about 25% 2-methyl branching, Dobanol and Neodolbeing Trade Names of Shell; Synperonics, which are understood to haveabout 50% 2-methyl branching, Synperonic being a Trade Name of I.C.I.;or the primary alcohols having more than 50% branched chain structuresold under the Trade Name Lial, by Liquichimica).

Other suitable nonionic surfactants are the polyethylene oxidecondensates of alkyl phenols. These include the condensation products ofalkyl phenols having an alkyl group containing from 6 to 12 carbonatoms, in either a straight or branched chain configuration, withethylene oxide. The ethylene oxide is preferably present in amountsequal to about 35 to about 100, more preferably about 40 to about 80,moles of ethylene oxide per mole of alkyl phenol. The alkyl substituentin such compounds may be derived, for example, from polymerisedpropylene, di-isobutylene, octene and nonene.

Nonionic surfactants suitable for use herein also include the compoundsformed by condensing ethylene oxide with a hydrophobic base. Thehydrophobic base is formed by the condensation of propylene oxide withpropylene glycol. The molecular weight of the hydrophobic portiongenerally falls in the range of about 1500 to 1800. Such syntheticnonionic detergents are items of commerce. They are available fromWyandotte Chemicals Corporation as "Pluronics".

Suitable polyethylene glycols are homopolymers of ethylene oxide havingthe general formula

    HO(C.sub.2 H.sub.4 O).sub.n H,

have an average molecular weight of from about 2,000 to about 15,000,preferably from about 3,000 to about 10,000 and most preferably fromabout 4,000 to about 8,000.

The fatty acids suitable for use in the bodies of the present inventioninclude the higher fatty acids containing from about 8 to about 24, andpreferably from about 12 to about 18, carbon atoms. It has also beenobserved that mixtures of fatty acids and nonionic binder materials,e.g., polyethylene glycols or nonionic surfactants, provide the bleachactivator with particularly good storage stability and dispersibility inthe wash water. It is believed that fatty acids reduce thehygroscopicity of the nonionic binder materials and that the nonionicbinder materials improve the dispersibility of the fatty acids. pH ofthe body can also be controlled with such materials when this isimportant.

Suitable anionic surfactants useful as binder or enrobing materials inthe bodies of the present invention include the water-soluble salts,preferably the alkali metal, ammonium and alkylolammonium salts, oforganic sulfuric reaction products having in their molecular structurean alkyl group containing from about 8 to about 20 carbon atoms and asulfonic or sulfuric acid ester group. (Included in the term "alkyl" isthe alkyl portion of acyl groups.) Examples of this group of syntheticsurfactants are the sodium and potassium alkyl sulfates, especiallythose obtained by sulfating the higher alcohols (C₈ -C₁₈ carbon atoms),and the sodium and potassium alkylbenzene sulfonates in which the alkylgroup contains from about 9 to about 15 carbon atoms in a straight orbranched chain configuration. These are described in U.S. Pat. Nos.2,220,099 and 2,477,383, both incorporated herein by reference. Thepreferred anionic surfactants are linear straight chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkylgroup is from about 11 to 13, abbreviated as C₁₁₋₁₃ LAS.

Other anionic surfactants useful as binder or enrobing materials in thebodies of the present invention are the water-soluble salts of thehigher fatty acids or "soaps". This includes alkali metal soaps such asthe sodium, potassium, ammonium, and alkylolammonium salts of the higherfatty acids containing from about 8 to about 24, and preferably fromabout 12 to about 18, carbon atoms. Soaps can be made by directsaponification of fats and oils or by the neutralization of free fattyacids.

Anionic surfactants useful as binder or enrobing materials in the bodiesof the present invention also include the the sodium alkyl glycerylether sulfonates, especially those ethers of higher alcohols derivedfrom tallow and coconut oil; sodium coconut oil fatty acid monoglyceridesulfonates and sulfates; sodium or potassium salts of alkyl phenolethylene oxide ether sulfates containing from about 1 to about 10 unitsof ethylene oxide per molecule or unit and wherein the alkyl groupscontain from about 8 to about 12 carbon atoms; and the sodium orpotassium salts of alkyl ethylene oxide ether sulfates containing about1 to about 10 units of ethylene oxide per molecule or unit and whereinthe alkyl groups contains from about 10 to about 20 carbon atoms.

Still other anionic surfactants useful as binder or enrobing materialsin the bodies of the present invention include the water-soluble saltsof the esters of alpha-sulfonated fatty acids containing from about 6 toabout 20 carbon atoms in the fatty acid group and from about 1 to about10 carbon atoms in the ester group; the water-soluble salts of2-acyloxyalkane-1-sulfonic acids containing from about 2 to about 9carbon atoms in the acyl group and from about 9 to about 23 carbon atomsin the alkane moiety; the water-soluble salts of olefin and paraffinsulfonates containing from about 12 to about 20 carbon atoms; andbeta-alkyloxy alkane sulfonates containing from about 1 to about 3carbon atoms in the alkyl group and from about 8 to about 20 carbonatoms in the alkane moiety.

Suitable film forming polymers useful as binder or enrobing materials inthe bodies of the present invention are the polymers derived from themonomers such as vinyl chloride, vinyl alcohol, furan, acrylonitrile,vinyl acetate, methyl acrylate, methyl methacrylate, styrene, vinylmethyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide,ethylene, propylene and 3-butenoic acid.

Preferred polymers of the above group are the homopolymers andcopolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid,which in the case of the copolymers contain at least about 50%, andpreferably at least about 80%, by weight, units derived from the acid.The particularly preferred polymer is sodium polyacrylate. Otherspecific preferred polymers are the homopolymers and copolymers ofmaleic anhydride, especially the copolymers with ethylene, styrene andvinyl methyl ether. These polymers are commercially available under thetrade names Versicol and Gantrez.

Other film-forming polymers useful as binder or enrobing materials inthe bodies of the present invention include the cellulose sulfate esterssuch as cellulose acetate sulfate, cellulose sulfate, hydroxyethylcellulose sulfate, methylcellulose sulfate and hydroxypropylcellulosesulfate.

Surprisingly, very small levels of binder or enrobing material withinthe body are required. The level of binder material useful within thebodies within the invention is from about 0.5% to about 50%, preferablyfrom about 2% to about 50%, and more preferably from about 4% to about15% by weight of the body.

Examples of preferred binder or enrobing materials include the fattyacid esters of alcohols, diols and polyols. For example, sorbitan fattyacid esters selected from the group sorbitan monolaurate, dilaurate,trilaurate, monopalmitate, monostearate, distearate, tristearate,monooleate, dioleate, and trioleate, are preferred. These materials areitems of commerce and are known as "Spans", a Trade Name of the I.C.I.Americas, Inc. Ethoxylated varieties of these compounds are also useful.For example, sorbitan esters having an average total level ofethoxylation of from about 4 to about 100, and preferably about 20 toabout 85 moles of ethylene oxide per mole of sorbitan, are preferred.

Particularly preferred binder materials include sorbitan monopalmitate,sorbitan monostearate, sorbitan distearate, and sorbitan tristearate.Polyethylene glycols having an average molecular weight of from about4,000 to about 8,000 are also useful and preferred. A mixture of lauricacid:PEG 8000, in a weight:weight ratio of about 2:1 to about 1:2, morepreferably about 1:1, is also preferred.

The binder or enrobing material need not be completely inert; the binderor enrobing material can be selected to benefit the overall bleachingactivity of the system. For example, employing 14%, by weight of a body,of C₁₃ LAS as the binder for the peroxygen bleach activator4-(2-chlorodecanoyloxo)benzenesulfonate can significantly increase therate of solubility of the peroxygen bleach activator.

The bodies of the present invention may also contain all of the usualcomponents of detergent compositions including the ingredients set forthin U.S. Pat. No. 3,963,537, Baskerville et al., incorporated herein byreference, so long as they are inert with respect to the bleachactivator and binder material. Such components include other peroxygenbleach activators, color speckles, suds boosters, suds suppressors,antitarnish and/or anticorrosion agents, soil-suspending agents,soil-release agents, dyes, fillers, optical brighteners, germicides,alkalinity sources, hydrotropes, antioxidants, enzymes, enzymestabilizing agents, perfumes, etc.

In a highly preferred embodiment, the bodies of the present inventioncomprise (a) from about 85% to about 96% of a peroxygen bleach activatorcompound having the general formula ##STR28## wherein R is a straight orbranched chain alkyl or alkenyl having from about 4 to about 14 carbonatoms; R¹ is H or C₂ H₅, X' is Cl, and L is selected from the groupconsisting of O--O--SO₃ ⁻ M⁺ and O--O--CO₂ ⁻ M⁺ wherein M is sodium orpotassium; and (b) about 4% to about 15% of a binder material selectedfrom the group consisting of sorbitan fatty acid esters, ethoxylatedvarieties of these sorbitan esters having an average total level ofethoxylation of from about 4 to about 8 moles of ethylene oxide per moleof sorbitan; linear alkylbenzenesulfonates in which the average numberof carbon atoms in the alkene moiety is about 11 to about 13; aliphaticalcohols containing between 9 and 18 carbon atoms ethoxylated withbetween 40 and 80 moles of ethylene oxide; sodium polyacrylate;polyethylene glycols having a molecular weight of from about 4000 toabout 8000, fatty acids containing from about 12 to about 18 carbonatoms; and mixtures thereof; the density of said body is from about 1.10g/cc to about 1.30 g/cc, said body contains less than about 1.5% waterand said body has an average particle size distribution of from about300 microns to about 1.5 millimeters.

REACTION METHOD

In accordance with the reaction method of the present invention, thealpha substituted alkylphenylsulfonates are prepared by contacting thecorresponding alpha-substituted acid chloride with disodiumphenolsulfonate under anhydrous conditions. A representation of thisreaction is as follows: ##STR29## wherein R is a straight or branchedchain alkyl or alkenyl having from about 2 to about 20 carbon atoms, Xis H, Cl, OCH₃ or OC₂ H₅, and R¹ is H or C₂ H₅. Preferred acid chloridesfor use in the methods of the present invention are those of the abovegeneral reaction formula wherein R is about 4 to about 12 carbon atoms,and more preferably about 6 to about 8 carbon atoms. Accordingly, thepresent process is particularly useful for preparing sodium4-(2-chlorooctanoyloxy)benzenesulfonate; sodium4-(2-chlorononanoyloxy)benzenesulfonate; sodium4-(2-chlorodecanoyloxy)benzenesulfonate; sodium4-(3,5,5-trimethyl-2-chlorohexanoyloxy)benzenesulfonate; sodium4-(2-chloro-2-ethylhexanoyloxy)benzenesulfonate; sodium2-(2-chlorooctanoyloxy)benzenesulfonate; sodium2-(2-chlorononanoyloxy)benzenesulfonate; and sodium2-(2-chlorodecanoyloxy)benzenesulfonate.

Both of the starting components necessary for the method of the presentinvention can be prepared by conventional means. The acid chloridestarting component may be prepared by conventional methods, or by theregiospecific methods described in U.S. Pat. No. 4,148,811, Crawford,issued Apr. 10, 1979; or U.S. Pat. No. 4,368,140, Crawford, issued Jan.11, 1983; both incorporated herein by reference. The alpha-substitutedcarboxylic acid may also be prepared employing the carboxylic acid,chlorine, a second strong acid, a free radical inhibitor and an organicacid anhydride as described in Example VI of the present specification.The alpha substituted carboxylic acid can then be converted byconventional means, such as reacting the carboxylic acid with SOCl₂,PCl₃ or PCl₅, and the like, to obtain the acid chloride. The secondstarting component, the disodium phenylsulfonate, can also be preparedby conventional means. As represented in Example IV, the monosodium saltcan be put into solution, an equivalent molar quantity of sodiumhydroxide is added, and the water removed.

The present process is not limited with regard to the method ofpreparing either of the starting components. The method employed toprepare either the acid chloride or the disodium phenolsulfonate playsno part in the practice of the present invention. For example, anunsubstituted acid chloride may be converted to an alpha-substitutedacid chloride according to Example II, column 7, lines 5-11 of U.S. Pat.No. 4,368,140, discussed above. The acid chloride so prepared can thenbe used as a starting component in the reaction of the presentinvention.

The process reaction herein can be carried out in the presence orabsence of inert solvents. For example, monoglyme, diglyme, toluene, andthe like, are good solvents for this reaction. Other useful solventsinclude dioxane, xylene, chlorobenzene, tetrahydrofuran andt-butyl-methylether. Preferably, the reaction is carried out with theuse of monoglyme or diglyme. These solvents are particularly useful dueto their boiling point, with monoglyme most preferred. The reaction iscarried out under anhydrous conditions. By anhydrous conditions, as usedherein, is meant that reaction environment or solvent is sufficientlyfree of water so that no side reactions take place. Preferably, anysolvent employed contains less than about 5%, more preferably less thanabout 1%, and most preferably less than about 0.5%, water, by weight ofsolvent.

The reaction process of this invention is exothermic. Accordingly, therate at which this reaction will proceed may be easily controlled bycontrolling the rate at which the heat is allowed to dissipate from thereaction environment. Because the heat from such a reaction is generallyconducted away via any solvent employed, selecting a solvent such asmonoglyme with a boiling point (760) of about 82°-83° C. allows thereaction temperature to be controlled by solvent. Under such conditions,the reflux takes place at the boiling point of the solvent and thetemperature is controlled accordingly. In turn, the rate of the reactionis also controlled.

While it is desirable to control the temperature of the reaction with asolvent, it is not necessary to do so. The reaction method of thepresent invention may be conducted and maintained at any temperaturewhich is high enough to allow the reaction to begin, but low enough toprevent decomposition of the desired product. Reactions of the presentinvention have reached temperatures of about 277° C. with no significantdisadvantages becoming apparent. However, it is preferred that thereaction methods of the present invention be commenced and maintained atabout 15° C. to about 150° C., more preferably about 15° C. to about100° C., and most preferably about 20° C. to about 100° C.

Typically, the molar ratio of alpha-substituted acid chloride:disodiumphenolsulfonate will be about 4:1 to about 1:4, and preferably about 2:1to about 1:2. Most preferably, the molar ratio of alpha-substituted acidchloride:disodium phenolsulfonate is about 1:1.

OPTIONAL COMPONENTS

As a preferred embodiment, the bleaching compositions of the inventioncan be formulated as laundry detergent compositions. Thus, the bleachingcompositions can contain typical detergent composition components andadjuvants. Such components include detergency surfactants and detergencybuilders. When used in such embodiments the bleaching compositions areparticularly effective.

The bleaching compositions of this invention can therefore contain allof the usual components of detergent compositions. This includes,without limitation, the ingredient set forth in U.S. Pat. No. 3,936,537,Baskerville, et al, issued Feb. 3, 1976, incorporated herein byreference. Such components, in addition to detergent surfactants andbuilders, include other peroxygen bleach activators, color speckles,suds boosters, suds suppressors, antitarnish and/or anticorrosionagents, soil-suspending agents, soil-release agents, dyes, fillers,optical brighteners, germicides, alkalinity sources, hydrotropes,antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.

DETERGENT SURFACTANTS

The amount of detergent surfactant included in the detergentcompositions of the present invention can vary from about 0% to about75%, by weight of the composition, depending upon the detergentsurfactant(s) used, the type of composition to be formulated (e.g.granular, liquid), the projected wash conditions and the effectsdesired. Preferably, the detergent surfactant(s) comprises from about10% to about 50%, by weight, more preferably from about 1% to about 30%,and most preferably from about 10% to about 25%, by weight, of the totalcomposition. However, because of the reactivity of the peroxygen bleachactivator compounds of the present invention, liquid detergentcompositions containing water should be formulated to stabilize thesecompounds.

The detergent surfactants which can be included in the bleachingcompositions of the present invention include any one or more surfaceactive agents selected from anionic, nonionic, zwitterionic, amphotericand cationic surfactants, and compatible mixtures thereof. Detergentsurfactants useful herein include, without limitation, those listed ordescribed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, U.S.Pat. No. 3,929,678, Laughlin, et al, issued Dec. 30, 1975, U.S. Pat. No.4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. No.4,239,659, Murphy, issued Dec. 16, 1980, all incorporated herein byreference. The following are representative examples of detergentsurfactants useful in the present compositions.

ANIONIC SURFACTANTS

Anionic surfactants suitable in detergent compositions of the presentinvention are generally disclosed in U.S. Pat. No. 3,929,678 to Laughlinet al., issued Dec. 30, 1975 at column 23, line 56 through column 29,line 23 (incorporated herein by reference). Classes of anionicsurfactants include the following.

Water-soluble salts of the higher fatty acids, i.e., "soaps", are usefulanionic surfactants in the present compositions. This includes alkalimetal soaps such as the sodium, potassium, ammonium, and alkylolammoniumsalts of higher fatty acids containing from about 8 to about 24 carbonatoms, and preferably from about 12 to about 18 carbon atoms. Soaps canbe made by direct saponification of fats and oils or by theneutralization of free fatty acids. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium or potassium tallow and coconut soap.

Useful anionic surfactants also include the water-soluble salts,preferably the alkali metal, ammonium and alkylolammonium salts, oforganic sulfuric reaction products having in their molecular structurean alkyl group containing from about 10 to about 20 carbon atoms and asulfonic acid or sulfuric acid ester group. (Included in the term"alkyl" is the alkyl portion of acyl groups.) Examples of this group ofsynthetic surfactants are the sodium and potassium alkyl sulfates,especially those obtained by sulfating the higher alcohols (alcoholshaving from about 8 to about 18 carbon atoms) such as those produced byreducing the glycerides of tallow or coconut oil; the sodium andpotassium alkylbenzene sulfonates in which the alkyl group contains fromabout 9 to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383, are also useful. Especially useful are thelinear straight chain alkylbenzene sulfonates in which the averagenumber of carbon atoms in the alkyl group is from about 11 to 13 carbonatoms, often abbreviated as C₁₁₋₁₃ LAS.

Other anionic surfactants useful in the bleaching compositions of thepresent invention are the sodium alkyl glyceryl ether sulfonates,especially those ethers (of higher alcohols) derived from tallow andcoconut oil; the sodium coconut oil fatty acid monoglyceride sulfonatesand sulfates; the sodium or potassium salts of alkyl phenol ethyleneoxide ether sulfates containing from about 1 to about 10 units ofethylene oxide per molecule and wherein the alkyl groups contain fromabout 8 to about 12 carbon atoms; and the sodium or potassium salts ofalkyl ethylene oxide ether sulfates containing about 1 to about 10 unitsof ethylene oxide per molecule and wherein the alkyl group contains fromabout 10 to about 20 carbon atoms.

Other anionic surfactants useful in the compositions of the presentinvention include the water-soluble salts of esters of alpha-sulfonatedfatty acids containing from about 6 to 20 carbon atoms in the fatty acidgroup and from about 1 to 10 carbon atoms in the ester group; thewater-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing fromabout 2 to 9 carbon atoms in the acyl group and from about 9 to about 23carbon atoms in the alkane moiety; the water-soluble salts of olefin andparaffin sulfonates containing from about 12 to 20 carbon atoms; and thebeta-alkyloxy alkane sulfonates containing from about 1 to 3 carbonatoms in the alkyl group and from about 8 to 20 carbon atoms in thealkane moiety.

NONIONIC SURFACTANTS

Suitable nonionic surfactants for use in detergent compositions of thepresent invention are generally disclosed in U.S. Pat. No. 3,929,678 toLaughlin et al., issued Dec. 30, 1975 at column 13, line 14 throughcolumn 16, line 6 (herein incorporated by reference). Useful classes ofnonionic surfactants useful in the compositions of the present inventioninclude the following.

1. The polyethylene oxide condensates of alkyl phenols. These compoundsinclude the condensation products of alkyl phenols having an alkyl groupcontaining from about 6 to 12 carbon atoms in either a straight chain orbranched chain configuration with ethylene oxide, the ethylene oxidebeing present in an amount equal to 5 to 25 moles of ethylene oxide permole of alkyl phenol. The alkyl substituent in such compounds can bederived, for example, from polymerized propylene, diisobutylene, and thelike. Examples of compounds of this type include nonyl phenol condensedwith about 9.5 moles of ethylene oxide per mole of nonyl phenol;dodecylphenol condensed with about 12 moles of ethylene oxide per moleof phenol; dinonyl phenol condensed with about 15 moles of ethyleneoxide per mole of phenol; and diisooctyl phenol condensed with about 15moles of ethylene oxide per mole of phenol. Commercially availablenonionic surfactants of this type include Igepal CO-630, marketed by theGAF Corporation, and Triton X-45, X-114, X-100, and X-102, all marketedby the Rohm & Haas Company.

2. The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from about 8 to about 22 carbon atoms. Examples ofsuch ethoxylated alcohols include the condensation product of myristylalcohol condensed with about 10 moles of ethylene oxide per mole ofalcohol; and the condensation product of about 9 moles of ethylene oxidewith coconut alcohol (a mixture of fatty alcohols with alkyl chainsvarying in length from 10 to 14 carbon atoms). Examples of commerciallyavailable nonionic surfactants of this type include Tergitol 15-S-9,marketed by Union Carbide Corporation, Neodol 45-9, Neodol 23-6.5,Neodol 45-7, and Neodol 45-4, marketed by Shell Chemical Company, andKyro EOB, marketed by The Proctor & Gamble Company.

3. The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of these compounds has a molecular weight of fromabout 1500 to 1800 and exhibits water insolubility. The addition ofpolyoxyethylene moieties to this hydrophobic portion tends to increasethe water solubility of the molecule as a whole, and the liquidcharacter of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product, which corresponds to condensation with up to about40 moles of ethylene oxide. Examples of compounds of this type includecertain of the commercially available Pluronic surfactants, marketed byWyandotte Chemical Corporation.

4. The condensation products of ethylene oxide with the productresulting from the reaction of propylene oxide and ethylenediamine. Thehydrophobic moiety of these products consists of the reaction product ofethylenediamine and excess propylene oxide, the moiety having amolecular weight of from about 2500 to about 3000. This hydrophobicmoiety is condensed with ethylene oxide to the extent that thecondensation product contains from about 40% to about 80% by weight ofpolyoxyethylene and has a molecular weight of from about 5,000 to about11,000. Examples of this type of nonionic surfactant include certain ofthe commercially available Tetronic compounds, marketed by WyandotteChemical Corporation.

5. Semi-polar nonionic detergent surfactants which include water-solubleamine oxides containing one alkyl moiety of from about 10 to 18 carbonatoms and 2 moieties selected from the group consisting of alkyl groupsand hydroxyalkyl groups containing from 1 to about 3 carbon atoms;water-soluble phosphine oxides containing one alkyl moiety of from about10 to 18 carbon atoms and 2 moieties selected from the group consistingof alkyl groups and hydroxyalkyl groups containing from about 1 to 3carbon atoms; and water-soluble sulfoxides containing one alkyl moietyof from about 10 to 18 carbon atoms and a moiety selected from the groupconsisting of alkyl and hydroxyalkyl moietes of from about 1 to 3 carbonatoms.

Preferred semi-polar nonionic detergent surfactants are the amine oxidedetergent surfactants having the formula ##STR30## wherein R³ is analkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereofcontaining from about 8 to about 22 carbon atoms; R⁴ is an alkylene orhydroxyalkylene group containing from 2 to 3 carbon atoms or mixturesthereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkylgroup containing from 1 to about 3 carbon atoms or a polyethylene oxidegroup containing from one to about 3 ethylene oxide groups. The R⁵groups can be attached to each other, e.g., through an oxygen ornitrogen atom to form a ring structure.

Preferred amine oxide detergent surfactants are C₁₀ -C₁₈ alkyl dimethylamine oxide and C₈ -C₁₂ alkoxy ethyl dihydroxy ethyl amine oxide.

6. Alkylpolysaccharides disclosed in U.S. application Ser. No. 371,747Ramon A. Llenado, filed Apr. 26, 1982, having a hydrophobic groupcontaining from about 6 to about 30 carbon atoms, preferably from about10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside,hydrophilic group containing an average of from about 11/2 to about 10,preferably from about 11/2 to about 3, most preferably from about 1.6 toabout 2.7 saccharide units. Any reducing saccharide containing 5 or 6carbon atoms can be used, e.g. glucose, galactose and galactosylmoieties can be substituted for the glucosyl moieties. (Optionally thehydrophobic group is attached to other positions, e.g. the 2-, 3-, 4-,positions etc., thus giving a glucose or galactose as opposed to aglucoside or galactoside.) The intersaccharide bonds can be, for examplebetween the 1-position of the additional saccharide units and the 2-,3-, 4-, and/or 6-positions on the preceding saccharide units.

Optionally, and less desirably, there can be a polyalkyleneoxide chainjoining the hydrophobic moiety and the polysaccharide moiety. Thepreferred alkyleneoxide is ethylene oxide. Typical hydrophobic groupsinclude alkyl groups, either saturated or unsaturated, branched orunbranched containing from about 8 to about 18, preferably from about 10to about 16, carbon atoms. Preferably, the alkyl group is a straightchain saturated alkyl group. The alkyl group can contain up to 3 hydroxygroups and/or the polyalkyleneoxide chain can contain up to about 10,preferably less than 5, most preferably 0, alkyleneoxide moieties.Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, andoctadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides,lactosides, glucoses, fructosides, fructoses, and/or galactoses.Suitable mixtures include coconut akyl, di-, tri-, tetra-, andpentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

The preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from 11/2 to about 10, preferably fromabout 11/2 to about 3, most preferably from about 1.6 to about 2.7. Theglycosyl is preferably derived from glucose. To prepare these compounds,the alcohol or alkylpolyethoxy alcohol is formed first and then reactedwith glucose, or a source of glucose, to form the glucoside (attachmentat the 1-position). The additional glycosyl units can then be attachedbetween their 1-position and the preceding glycosyl units 2-, 3-, 4-and/or 6-position, preferably predominately the 2-position.

7. Fatty acid amide detergent surfactants having the formula: ##STR31##wherein R⁶ is an alkyl group containing from about 7 to about 21(preferably from about 9 to about 17) carbon atoms and each R⁷ isselected from the group consisting of hydrogen, C₁ -C₄ alkyl, C₁ -C₄hydroxyalkyl, and --(C₂ H₄ O)_(x) H where x varies from about 1 to about3.

Preferred amides are C₈ -C₂₀ ammonia amides, monoethanolamides,diethanolamides, and isopropanol amides.

Ampholytic surfactants can be broadly described as derivatives ofaliphatic or aliphatic derivatives of heterocyclic secondary andtertiary amines in which the aliphatic moiety can be straight chain orbranched and wherein one of the aliphatic substituents contains fromabout 8 to 18 carbon atoms and at least one aliphatic substituentcontains an anionic water-solubilizing group. See U.S. Pat. No.3,929,678, Laughlin, et al., issued Dec. 30, 1975 at column 19, line 38through column 22, line 48 for examples of ampholytic surfactants.

ZWITTERIONIC SURFACTANTS

Zwitterionic surfactants can be broadly described as derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No.3,929,678, Laughlin, et al., issued Dec. 30, 1975 at column 19, line 38through column 22, line 48 (incorporated herein by reference) forexamples of zwitterionic surfactants.

CATIONIC SURFACTANTS

Cationic surfactants can also be included in detergent compositions ofthe present invention. Suitable cationic surfactants include thequaternary ammonium surfactants having the formula:

    [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ].sub.2 R.sup.5 N.sup.+ X.sup.-

wherein R² is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain; each R³ is selected from thegroup consisting of --CH₂ CH₂ --, --CH₂ CH(CH₃)--, CH₂ CH(CH₂ OH)--,--CH₂ CH₂ CH₂ --, and mixtures thereof; each R⁴ is selected from thegroup consisting of C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, benzyl, ringstructures formed by joining the two R⁴ groups, --CH₂ CHOHCHOH--COR⁶CHOHCH₂ OH wherein R⁶ is any hexose or hexose polymer having a molecularweight less than about 1000, and hydrogen when y is not 0; R⁵ is thesame as R⁴ or is an alkyl chain wherein the total number of carbon atomsof R² plus R⁵ is not more than about 18; each y is from 0 to about 10and the sum of the y values is from 0 to about 15; and X is anycompatible anion.

Preferred of the above are the alkyl quaternary ammonium surfactants,especially the mono-long chain alkyl surfactants described in the aboveformula when R⁵ is selected from the same groups as R⁴. The mostpreferred quaternary ammonium surfactants are the chloride, bromide andmethylsulfate C₈ -C₁₆ alkyl trimethylammonium salts, C₈ -C₁₆ alkyldi(hydroxyethyl)methylammonium salts, the C₈ -C₁₆ alkylhydroxyethyldimethylammonium salts, and C₈ -C₁₆ alkyloxypropyltrimethylammonium salts. Of the above, decyl trimethylammoniummethylsulfate, lauryl trimethylammonium chloride, myristyltrimethylammonium methylsulfate and coconut trimethylammonium chlorideand methylsulfate are particularly preferred. The use of bromides isleast preferred due to the possible formation of hypobromite.

DETERGENT BUILDERS

In addition to detergent surfactants, detergency builders can beemployed in the bleaching compositions of the present invention. Whenincluded, the level of detergency builder of the bleaching compositionsis from 0% to about 80%, preferably from about 10% to about 60%, byweight, and most preferably from about 20% to about 60%, by weight ofthe composition. Water-soluble inorganic or organic electrolytes aresuitable builders. The builder can also be water-insoluble calcium ionexchange materials; nonlimiting examples of suitable water-soluble,inorganic detergent builders include: alkali metal carbonates, borates,phosphates, bicarbonates and silicates. Specific examples of such saltsinclude sodium and potassium tetraborates, bicarbonates, carbonates,orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates.

Suitable detergent builders include crystalline aluminosilicate ionexchange materials having the formula:

    Na.sub.z [(AlO.sub.2).sub.z.(SiO.sub.2).sub.y ].xH.sub.2 O

wherein z and y are at least about 6, the mole ratio of z to y is fromabout 1.0 to about 0.5; and x is from about 10 to about 264. Amorphoushydrated aluminosilicate materials useful herein have the empiricalformula

    M.sub.z (zAlO.sub.2. ySiO.sub.2)

wherein M is sodium, potassium, ammonium or substituted ammonium, z isfrom about 0.5 to about 2; and y is 1; this material having a magnesiumion exchange capacity of at least about 50 milligram

The aluminosilicate ion exchange builder materials are in hydrated formand contain from about 10% to about 28% of water by weight ifcrystalline, and potentially even higher amounts of water if amorphous.Highly preferred crystalline aluminosilicate ion exchange materialscontain from about 18% to about 22% water in their crystal matrix. Thepreferred crystalline aluminosilicate ion exchange materials are furthercharacterized by a particle size diameter of from about 0.1 micron toabout 10 microns. Amorphous materials are often smaller, e.g., down toless than about 0.01 micron. More preferred ion exchange materials havea particle size diameter of from about 0.2 micron to about 4 microns.The term "particle size diameter" represents the average particle sizediameter of a given ion exchange material as determined by conventionalanalytical techniques such as, for example, microscopic determinationutilizing a scanning electron microscope. The crystallinealuminosilicate ion exchange materials are usually further characterizedby their calcium ion exchange capacity, which is at least about 200 mg.equivalent of CaCO₃ water hardness/g. of aluminosilicate, calculated onan anhydrous basis, and which generally is in the range of from about300 mg. eq./g. to about 352 mg. eq./g. The aluminosilicate ion exchangematerials are still further characterized by their calcium ion exchangerate which is at least about 2 grains Ca⁺⁺ /gallon/minute/gram/gallon ofaluminosilicate (anhydrous basis), and generally lies within the rangeof from about 2 grains/gallon/minute/gram/gallon to about 6grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimumaluminosilicates for builder purposes exhibit a calcium ion exchangerate of at least about 4 grains/gallon/minute/gram/gallon.

The amorphous aluminosilicate ion exchange materials usually have a Mg⁺⁺exchange capacity of at least about 50 mg. eq. CaCO₃ /g. (12 mg. Mg⁺⁺/g.) and a Mg⁺⁺ exchange rate of at least about 1grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit anobservable diffraction pattern when examined by Cu radiation (1.54Angstrom Units).

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal., issued Oct. 12, 1976 (herein incorporated by reference). Preferredsynthetic crystalline aluminosilicate ion exchange materials usefulherein are available under the designations Zeolite A, Zeolite P (B),and Zeolite X. In an especially preferred embodiment, the crystallinealuminosilicate ion exchange material has the formula

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27.

Other examples of detergency builders include the various water-soluble,alkali metal, ammonium or substituted ammonium phosphates,polyphosphates, phosphonates, polyphosphonates, carbonates, silicates,borates, polyhydroxysulfonates, polyacetates, carboxylates, andpolycarboxylates. Preferred are the alkali metal, especially sodium,salts of the above.

Examples of suitable organic alkaline detergency builders include: (1)water-soluble amino carboxylates and aminopolyacetates, for example,nitrilotriacetates, glycinates, ethylenediamine tetraacetates,N-(2-hydroxyethyl)nitrilo diacetates and diethylenetriaminepentaacetates; (2) water-soluble salts of phytic acid, for example,sodium and potassium phytates; (3) water-soluble polyphosphonates,including sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium, and lithium salts of ethylenediphosphonic acid; and the like; (4) water-soluble polycarboxylates suchas the salts of lactic acid, succinic acid, malonic acid, maleic acid,citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3,-propanetricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, mellitic acidand pyromellitic acid; and (5) the water-soluble polyacetals asdisclosed in U.S. Pat. Nos. 4,144,266 and 4,246,495, incorporated hereinby reference.

Specific examples of inorganic phosphate builders are sodium andpotassium tripolyphosphate, pyrophosphate, polymeric metaphosphatehaving a degree of polymerization of from about 6 to 21, andorthophosphate. Examples of polyphosphonate builders are the sodium andpotassium salts of ethylene-1,1-diphosphonic acid, the sodium andpotassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodiumand potassium salts of ethane, 1,1,2-triphosphonic acid. Otherphosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581;3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148 (allincorporated herein by reference).

Examples of nonphosphorus, inorganic builders are sodium and potassiumcarbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, andsilicate having a mole ratio of SiO₂ to alkali metal oxide of from about0.5 to about 4.0, preferably from about 1.0 to about 2.4.

Useful water-soluble, nonphosphorus organic builders include the variousalkali metal, ammonium and substituted ammonium polyacetates,carboxylates, polycarboxylates and polyhydroxysulfonates. Examples ofpolyacetate and polycarboxylate builders are the sodium, potassiumlithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melliticacid, benzene polycarboxylic acids, and citric acid.

Highly preferred polycarboxylate builders are disclosed in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967, incorporated herein by reference.Such materials include the water-soluble salts of homo and copolymers ofaliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconicacid, fumaric acid, aconitic acid, citraconic acid and methylenemalonicacid.

Other builders include the carboxylated carbohydrates disclosed in U.S.Pat. No. 3,723,322, Diehl, issued Mar. 28, 1973, incorporated herein byreference.

Other useful builders are sodium and potassium carboxymethyloxymalonate,carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate,cis-cyclopentanetetracarboxylate phloroglucinol trisulfonate,water-soluble polyacrylates (having molecular weights of from about2,000 to about 200,000 for example), and the copolymers of maleicanhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylatesdisclosed in U.S. Pat. No. 4,144,226, Crutchfield, et al., issued Mar.13, 1979, and U.S. Pat. No. 4,246,495, Crutchfield, et al., issued Mar.27, 1979, both incorporated herein by reference. These polyacetalcarboxylates can be prepared by bringing together under polymerizationconditions an ester of glyoxylic acid and a polymerization initiator.The resulting polyacetal carboxylate ester is then attached tochemically stable end groups to stabilize the polyacetal carboxylateagainst rapid depolymerization in alkaline solution, converted to thecorresponding salt, and added to a surfactant.

Another type of detergency builder material useful in the presentcompositions comprises a water-soluble material capable of forming awater-insoluble reaction product with water hardness cations. Thispreferably occurs in combination with a crystallization seed which iscapable of providing growth sites for said reaction product. Such"seeded builder" compositions are fully disclosed in British PatentSpecification No. 1,424,406, incorporated herein by reference. Otheruseful detergency builder materials are the "seeded builder"compositions disclosed in Belgian Pat. No. 798,856, issued Oct. 29,1973, incorporated herein by reference. Specific examples of such seededbuilder mixtures are: 3:1 wt. mixtures of sodium carbonate and calciumcarbonate having 5 micron particle diameter; 2.7:1 wt. mixtures ofsodium sesquicarbonate and calcium carbonate having a particle diameterof 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonate and calciumhydroxide having a particle diameter of 0.01 micron; and a 3:3:1 wt.mixture of sodium carbonate, sodium aluminate and calcium oxide having aparticle diameter of 5 microns.

ADDITIONAL OPTIONAL COMPONENTS

Buffering agents can be utilized to maintain the desired alkaline pH ofthe bleaching solutions. Buffering agents include, without limitation,the detergency builder compounds disclosed herein. Buffering agentssuitable for use in the bleaching compositions of the present inventionare well known in the detergency art.

Preferred optional ingredients include suds modifiers, particularlythose of suds suppressing types. These include, for example, siliconesand silica-silicone mixtures. U.S. Pat. Nos. 3,933,672, issued Jan. 20,1976 to Bartolotta et al, and 4,136,045, issued Jan. 23, 1979 to Gaultet al, incorporated herein by reference, disclose silicone sudscontrolling agents. The silicone material can be represented byalkylated polysiloxane materials such as silica aerogels and xerogelsand hydrophobic silicas of various types. The silicone material can bedescribed as siloxane having the formula: ##STR32## wherein x is fromabout 20 to about 2,000 and R and R¹ are each alkyl or aryl groups,especially methyl, ethyl, propyl, butyl and phenyl. Thepolydimethylsiloxanes (i.e., compounds of the above formula wherein Rand R¹ are methyl) having a molecular weight of from about 200 to about2,000,000 (and higher) are all useful as suds controlling agents.Additional suitable silicone materials wherein the side chain groups Rand R¹ are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups,exhibit useful suds controlling properties. These include diethyl-,dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpoly-siloxanes, andthe like. Additional useful silicone suds controlling agents can berepresented by a mixture of an alkylated siloxane, as referred tohereinbefore, and solid silica. Such mixtures are prepared by affixingthe silicone to the surface of the solid silica. A preferred siliconesuds controlling agent is represented by a hydrophobic silanated (mostpreferably trimethylsilanated) silica having a particle size in therange from about 10 millimicrons to 20 millimicrons and a specificsurface area above about 50 m² /gm. intimately admixed with dimethylsilicone fluid having a molecular weight in the range from about 500 toabout 200,000 at a weight ratio of silicone to silanated silica of fromabout 19:1 to about 1:2. The silicone suds suppressing agent isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-activedetergent-impermeable carrier.

Particularly useful suds suppressors are the self-emulsifying siliconesuds suppressors, described in U.S. Pat. No. 4,073,118, Gault et al,issued Feb. 21, 1978, incorporated herein by reference. An example ofsuch a compound is DB-544, commercially available from Dow-Corning,which is a siloxane/glycol copolymer.

Suds modifiers as described above are used at levels of 0% to about 2%,preferably from about 0.1 to about 1.5% by weight of the surfactant.

Microcrystalline waxes having a melting point in the range from 35°C.-115° C. and a saponification value of less than 100 representadditional examples of preferred suds control components for use in thebleaching compositions of the present invention. These are described indetail in U.S. Pat. No. 4,056,481, Tate, issued Nov. 1, 1977,incorporated herein by reference. The microcrystalline waxes aresubstantially water-insoluble, but are water-dispersible in the presenceof organic surfactants. Preferred microcrystalline waxes have a meltingpoint from about 65° C. to 100° C., a molecular weight in the range from400-1,000, and a penetration value of at least 6, measured at 77° F. byASTM-D1321. Suitable examples of the above waxes include:microcrystalline and oxidized microcrystalline petroleum waxes;Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin;montan wax; beeswax; candelilla; and carnauba wax.

Alkyl phosphate esters represent an additional preferred suds controlagent for use herein. These preferred phosphate esters are predominantlymonostearyl phosphate which, in addition thereto, can contain di- andtristearyl phosphates and monooleyl phosphate, which can contain di- andtrioleyl phosphate.

Other suds control agents useful in the practice of the invention arethe soap or the soap and nonionic mixtures as disclosed in U.S. Pat.Nos. 2,954,347 and 2,954,348, incorporated herein by reference.

The following examples are given to illustrate the parameters of andcompositions within the invention. All percentages, parts and ratios areby weight unless otherwise indicated.

EXAMPLE I

The following bleaching/granular detergent compositions and systems wereformulated using conventional procedures and techniques. When employedin conventional procedures for overall performance testing (such as thedescribed in Example I of U.S. Pat. No. 4,412,934, Chung, et al., issuedNov. 1, 1983) or in typical washing procedures, excellent bleachingperformance is obtained.

    ______________________________________                                        BLEACH COMPOSITIONS/SYSTEMS                                                   ______________________________________                                        A   Sodium perborate alone                                                    B   Sodium perborate monohydrate                                                  Sodium 4-(2-chlorobutanoyloxo)benzene sulfonate                           C   Sodium perborate monohydrate                                                  Sodium 4-(2-chlorooctanoyloxo)benzene sulfonate                           D   Sodium perborate monohydrate                                                  Sodium 4-(2-chlorononanoyloxo)benzene sulfonate                           E   Sodium perborate monohydrate                                                  Sodium 4-(2-chlorodecanoyloxo)benzene sulfonate                           F   Sodium perborate monohydrate                                                  Sodium 4-(3,5,5-trimethyl-2-chlorohexanoyloxo)benzene sul-                    fonate                                                                    G   Sodium perborate monohydrate                                                  Sodium 4-(2-chloro-2-ethylhexanoyloxo)benzene sulfonate                   H   Sodium perborate monohydrate                                                  Sodium 2-(2-chlorononanoyloxo)benzoate                                    I   Sodium perborate monohydrate                                                  Sodium 4-(2-methoxydecanonyloxo)benzene sulfonate                         J   Sodium perborate monohydrate                                                  Sodium 4-(2 methoxydodecanoyloxo)benzene sulfonate                        ______________________________________                                    

The following granular detergent composition is prepared to be used withthe above indicated systems and other bleach compositions of the presentinvention:

    ______________________________________                                                            Parts by Weight                                           ______________________________________                                        Sodium C.sub.14-15 alkyl/alkylethoxy sulfate                                                        8.75                                                    C.sub.12-13 linear alkyl primary                                                                    8.75                                                    alcohol ethoxylate.sub.6.5T*                                                  C.sub.12 alkyltrimethyl ammonium chloride                                                           1.0                                                     Sodium tripolyphosphate                                                                             37.0                                                    Sodium diethylenetriamine penta-acetate                                                             1.0                                                     Sodium carbonate      14.0                                                    Sodium sulfate        11.5                                                    Silicon dioxide (SiO.sub.2) (1.6r)                                                                  6.0                                                     Water                 7.0                                                     Bleach Composition C  12.0                                                    Miscellaneous (e.g., perfumes, enzymes,                                                             1.8                                                     suds supressors, optical brighteners, etc.)                                   ______________________________________                                         *Stripped of lower ethoxylated fractions and fatty alcohol.              

The above granular detergent composition is used employing 12 parts ofthe bleach composition for each treatment at the suggested ratios. Allingredients of the final detergent composition are added to the washsimultaneously. The overall order of addition is water-fabrics-testcomposition. In some cases, the activator may be dissolved in waterbefore addition.

Bleach Composition C in the detergent composition above is replaced, inwhole or in part, by Bleach Compositions D-J, or mixtures thereof, andsimilar bleaching performance is obtained. Further, various ratios ofperborate (total):bleach activator (total), by weight of thecomposition, may be employed: 1:1, 3:1, 1:2, 1:3 and 6:5; good bleachingperformance is obtained at these ratios for single systems, and formixtures of such systems.

The peroxygen bleach activator compounds of the above systems and BleachCompositions are replaced, in part, by a second conventional activator,at a ratio of alpha substituted peroxygen bleach activator:secondactivator of about 3:1 to about 1:3. When such conventional activator isselected from the group consisting of sodium4-octanoyloxybenzenesulfonate; sodium 4-nonanoyloxybenzenesulfonate;tetra acetyl glycouril; tetra acetyl ethylene diamine; and tetra acetylmethylene diamine, similar bleaching performance is obtained.

The sodium perborate monohydrate of the above Bleach Compositions andsystems is replaced, in whole or in part, at a perborate (total):bleachactivator ratio of about 1:3 to about 3:1, by one or more peroxygenbleach compounds selected from the group consisting of sodium perboratetetrahydrate; sodium carbonate peroxyhydrate; sodium pyrophosphateperoxyhydrate, urea peroxyhydrate, and sodium peroxide; similarbleaching performance is obtained.

EXAMPLE II Preparation of Bodies Containing Peroxygen Bleach Activator

87 parts of the selected peroxygen bleach activator ingredient(alpha-substituted alkyl oxybenzene sulfonate) is thoroughly mixed withthe binder or coating (Sorbitan monopalmitate) in a warm container70°-75° C. (160°-170° F.) until a homogeneous doughy consistency isachieved. This mixture is then forced through a warmed 70°-75° C.(160°-170° F.) orifice (approximately 1.5 mm diameter) to produce longnoodles. After cooling to room temperature these are then cut into 1.5-3mm lengths and screened (24 mesh) to remove fine particulate matter anddust resulting from the cutting operation. The final material is thenadded to, mixing thoroughly, a granular detergent composition such asthat described in Example I.

The binder material above is replaced, in whole or in part, by C₁₃ LAS,C₁₂ LAS, C₁₁ LAS, sorbitan monolaurate, sorbitan monostearate, sorbitanmonooleate, a 1:1 mixture (by weight) of PEG 8000:lauric acid, sodiumpolyacrylate and sodium methacrylate; similar stability is obtained.

EXAMPLE III Preparation of Disodium p-Phenolsulfonate ##STR33##

Disodium p-phenolsulfonate was prepared by adding a solution of 483.5 g(12.1 moles) of sodium hydroxide in 750 ml of water to 2784 g (12.0mole) of the monosodium salt dihydrate dispersed in 2 l. of water. Thefinal pH of this mixture was 10.6. Most of the water was evaporated in arotary evaporator and the resulting rigid solid was transferred to avacuum oven for final drying at 115°-120° C. (100 hours in thisexample). The anhydrous disodium salt weighed 2607 g (99.6% yield).

Preparation of Sodium 4-(2-chlorooctanoyloxy)benzene sulfonate

Anhydrous disodium p-phenolsulfonate (221 g; 1.015 moles) was slurriedin 500 ml of dry diglyme (diethylene glycol dimethylether) in a 1 l,three-necked flask equipped with a mechanical stirrer, thermometer andan inert gas inlet. This mixture was warmed to 48° C. and 200 g (1.015moles) of 2-chlorooctanoyl chloride was added, dropwise or in a thinstream, at such a rate that the temperature did not rise substantiallyabove 100° C. The reaction mixture was cooled occasionally during theacid chloride addition. After the acid chloride had been added, themixture was stirred for two hours at which time a thin layerchromatogram and a proton nmr spectrum showed that the reaction wasessentially complete.

The thick mixture was then diluted with ether to give an easily pourableslurry which was filtered. The product (filter cake) was reslurried in1.5 l of ether and filtered again. Recrystallization from 3.5 l of 20%aqueous methanol gave 280 g (77% yield) of sodium4-(2-chlorooctanoyloxy)benzene sulfonate as lustrous white flakes. Bythin layer chromatography, infrared and nmr spectroscopy the product wasvirtually free of starting materials or side products. Elementalanalysis indicated it contained 0.44% NaCl.

EXAMPLE IV Preparation of Sodium 4-(decanoyloxy)benzene sulfonate

Decanoyl chloride (19.1 g; 0.10 mole) was added all at once to a slurryof 21.8 g (0.10 mole) of anhydrous disodium phenolsulfonate and 50 ml ofdry monoglyme contained in a 500 ml round-bottomed flask protected frommoisture. A modest exotherm occurred and the reaction mixture wasstirred at ambient temperature overnight. A thin layer chromatogramindicated that the reaction was essentially complete, and the thickcreamy mixture was diluted with ether and filtered. The solids wererinsed with additional ether, were sucked dry, and the product was thenrecrystallized from 500 ml of 10% aqueous methanol. The sodiump-decanoyloxybenzene sulfonate was collected by filtration and dried togive 34.6 g (99%) of pearly flakes. Elemental, thin layerchromatographic, infrared and nuclear magnetic resonance analysesindicated that the product was essentially free of sodium chloride,starting materials or other by-products.

EXAMPLE V Preparation of Sodium 4-(2-chlorononanoyloxy)benzene sulfonate

Anhydrous disodium p-phenolsulfonate (28.5 g; 0.130 mole) and 30.3 g(0.1436 mole) of 2-chlorononanoyl chloride were combined in a 500 mlround-bottomed flask. The flask was then immersed in an oil bath whichhad been preheated to 110° C. Within five minutes an exothermic reactingoccurred which caused the entire mixture to congeal. After cooling, themixture was triturated three times with 150-200 ml portions of ether andthe product was vacuum dried. Elemental and nmr analyses of theresulting tan powder, 46.2 g, indicated that it was composed of 11.5%NaCl, 17.7% disodium p-phenolsulfonate, and 70.8% of sodiump-(2-chlorononanoyloxy)benzene sulfonate. This represents a 68% yield ofthe desired product.

EXAMPLE VI Preparation of 2-Chloroalkyl Acid

A one-liter, three-necked round bottom reaction flask was mounted in afume hood and placed in a 335 watt heating mantle. A mechanical stirrer,dry ice condenser and a fritted gas dispersion tube were fitted to thereaction flask. The temperature of the reaction flask was controlled byuse of a Thermo-Watch which maintains the function of a Jack-O-Matic,upon which the heating mantle was placed. The dispersion tube wasconnected to a chlorine source by PVC tubing and metered with an in lineflowmeter having a range of 0.05 to 1 liter/min.

The reaction vessel was initially charged with 1.0 mole of stearic acid(284.5 grams). The stearic acid was melted by raising the temperature to80° C. At this time 0.005 mole TCNQ (1.02 grams) was added to thereaction vessel. Chlorine gas at a flow rate of 0.05 liter/min. wasadded to solubilize the TCNQ into the melted stearic acid. Aceticanhydride at a 0.06 molar level (6.125 grams) was then added to thereaction flask and the temperature was rapidly elevated to 130° C. Usinga pipette, 0.016 mole sulfuric acid (1.6 grams) was then added to thereaction vessel. The temperature was then adjusted to 150° C. and thechlorine flow rate was adjusted to 0.5 liter/min. This point wasconsidered time zero for the beginning of the reaction.

After 52 minutes of reaction time, the chlorine flow rate was readjustedto 0.05 liter/min. and the reaction mixture was slowly cooled under ahead of chlorine gas to the product melting point (64° C.).

After cooling, the reaction product was analyzed by gas chromatographyas being 96.12% 2-chlorostearic acid, 2.71% 2,2-dichlorostearic acid,0.42% free radical chlorination products, and 0.75% unreacted stearicacid.

If the above reaction is carried out with fatty acids having alkyl chainlengths from 8 to 18 carbons, or combinations thereof, the corresponding2-chloroalkyl acids are produced in purities exceeding 95%. Thesematerials may then be employed as follows:

Preparation of 4-(2-chlorononanoyloxy)benzenesulfonate

The reaction was carried out in a 12 l flask equipped with a heavy dutypaddle stirrer, reflux condenser, addition funnel, thermometer, heatingmantle and inert gas inlet.

A slurry of 2237 g (10.26 moles) of disodium p=phenolsulfonate in agallon of dry 1,2-dimethoxyethane(monoglyme) was warmed to 50° C. Theheating mantle was switched off and the addition of 2169 g (10.28 moles)of 2-chlorononaoyl chloride was begun. The rate of addition was suchthat a steady reflux was maintained. As the reaction proceeded, itthickened and after 80 minutes, with about 80-85% of the acid chlorideadded, another 500 ml of solvent was added to improve stirring. The acidchloride addition was complete within 1.5 hours after which the mixturewas allowed to stand overnight.

Ether (3 l) was added to give a thinner slurry and the crude product wascollected by vacuum filtration. By nmr, the crude product contained 88mole percent product and 12 mole percent starting phenolsulfonate (plussalts).

Recrystallization was carried out, batchwise, from a total of 65 l of12.5% aqueous methanol at 5° C. There was obtained 2672 g (70% yield) offirst crop product as lustrous while flakes. Concentration of the motherliquor followed by another recrystallization gave a second crop (330 g)which brought the recovered yield to 79%.

EXAMPLE VII

A base detergent product was prepared with the following composition:

    ______________________________________                                        Base Product            %                                                     ______________________________________                                        Sodium C.sub.14-15 alkyl sulfate                                                                      7.5                                                   Sodium C.sub.13 linear alkylbenzene sulfonate                                                         7.5                                                   C.sub.12 alkyltrimethyl ammonium chloride                                                             1.0                                                   C.sub.12-13 alkyl polyethoxylate.sub.6.5T                                                             1.0                                                   Sodium silicate         5.0                                                   Sodium tripolyphosphate 32.0                                                  Sodium sulfate          11.2                                                  Sodium carbonate        16.0                                                  Miscellaneous (e.g., perfume, optical                                                                 Balance                                               brightener, protease enzyme, suds                                             suppressor, chelating agent, polyethylene                                     glycol, etc.)                                                                 ______________________________________                                    

Various mixtures of the activators sodium 4-nonanoyloxybenzene sulfonateand sodium 4-(2-chlorononanoyloxy)benzene sulfonate (hereinafter NOBSand alpha-chloro NOBS) were added along with the peroxygen bleachcompound, sodium perboarate monohydrate (hereinafter PB1), to the basedetergent product in the amounts indicated below. The resultingdetergent products were then tested in full scale washers, using 1500parts per million (ppm) of product, a water temperature of 95° F. (35°C.) and a water hardness of 5 grains per gallon, respectively.

A panel of expert graders compared the cleaning performance of theproducts on selected stains using a scale in which 0 means "There is nodifference"; 1 means "I think I see a difference"; 2 means "I see adifference"; and 3 means "I see a big difference". The results inaverage panel score units (PSU) versus a control, which contains 4% NOBSand 3.5% PB1, were as follows:

    ______________________________________                                                 alpha-  80:20 alpha-                                                                              60:40 alpha-                                              Chloro  Chloro NOBS:                                                                              Chloro NOBS:                                     Activator                                                                              NOBS    NOBS        NOBS      LSD.sub.95                             ______________________________________                                        Activ. Level                                                                            4.0%    4.0%         4.0%                                           PB1 Level                                                                               3.5%    3.5%         3.5%                                           Stain PSU grades vs. 4% NOBS/3.5% PB1                                         Dingy    0.1     0.1         -0.1      0.56                                   T-shirts                                                                      Dingy    0.2     0.2         -0.1      0.62                                   pillow cases                                                                  Carrot juice                                                                           -3.4    -2.3        -1.3      1.52                                   Barbeque -3.1    -1.9        -1.3      1.89                                   Spaghetti                                                                              -1.4    -1.3        -0.8      2.25                                   ______________________________________                                                60:40      40:60      20:80                                                   alpha-Chloro                                                                             alpha-Chloro                                                                             alpha-Chloro                                            NOBS:      NOBS:      NOBS:                                           Activator                                                                             NOBS       NOBS       NOBS     LSD.sub.95                             ______________________________________                                        Activ.    4.0%      4.0%        4.0%                                          Level                                                                         PB1       3.5%      3.5%        3.5%                                          Level                                                                         Stain PSU grades vs. 4% NOBS/3.5% PB1                                         Dingy   -0.1       0.3        -0.3     0.68                                   T-shirts                                                                      Pillow  -0.1       0.0         0.1     0.52                                   cases                                                                         Carrot  -2.6       -1.7       -1.1     2.19                                   juice                                                                         Barbeque                                                                              -1.3       -0.9       -0.4     2.57                                   Spaghetti                                                                              0.4       -0.2        0.5     2.65                                   ______________________________________                                    

As shown above, mixtures of alpha-chloro NOBS and NOBS provide effectivebleaching; showing improvement in bleaching activity from 100% NOBSactivator.

EXAMPLE VIII

The base product and testing conditions were as per Example VII. Theamount of perborate was varied to show the effect of reducing perborateusage at constant mixed NOBS activator levels.

    ______________________________________                                                  60:40 alpha- 60:40 alpha-                                                     Chloro NOBS: Chloro NOBS:                                           Activator NOBS         NOBS        LSD.sub.95                                 ______________________________________                                        Activ. Level                                                                              4.0%         4.0%                                                 Perborate Level                                                                           3.5%         2.7%                                                 Stain PSU vs. 4% NOBS/3.5% PB1                                                Dingy     -0.2         -0.1        0.64                                       T-shirts                                                                      Pillow    --           --          --                                         cases                                                                         Carrot juice                                                                            -0.8         -1.4        1.36                                       Barbeque  -1.4         -0.7        1.35                                       Spaghetti -0.2         -0.5        1.10                                       ______________________________________                                                60:40      60:40      60:40                                                   alpha-Chloro                                                                             alpha-Chloro                                                                             alpha-Chloro                                            NOBS:      NOBS:      NOBS:                                           Activator                                                                             NOBS       NOBS       NOBS     LSD.sub.95                             ______________________________________                                        Activ.    4.0%       4.0%       4.0%                                          Level                                                                         PB1       3.5%       1.9%       1.0%                                          Level                                                                         Stain PSU grades vs. 4% NOBS/3.5% PB1                                         Dingy   -0.1        0.1       -0.3     0.29                                   T-shirts                                                                      Dingy    0.1       -0.3       -0.2     0.48                                   pillow cases                                                                  Carrot  -2.6       -2.3       -2.2     1.41                                   juice                                                                         Barbeque                                                                              -2.1       -1.6       -1.0     1.99                                   Spaghetti                                                                             -0.3       -0.7       -1.3     3.09                                   ______________________________________                                    

As shown above, the 60:40 alpha-chloro mixed activator shows effectivebleaching even when the perborate levels are reduced significantly.

EXAMPLE IX

An odor profile evaluation of alpha-chloro NOBS, NOBS, and mixed NOBSwas performed by trained perfumers.

The base product of Example VII was used. The peroxygen bleach compoundand varying activator mixtures were added as indicated below, and theresulting detergent products were tested in automatic mini washers using1500 ppm of product at water temperature of 125° F. (52° C.) and a waterhardness of 5 grains per gallon, respectively. Soiled fabrics were addedto the wash any special conditions are noted below.

Odor profiles were then evaluated by trained perfumers, who ranked themfrom 1 to 5 in order of preference.

    ______________________________________                                        Treatment                                                                              Ranking    Odor Characteristics                                      ______________________________________                                        Test #1 (Special condition: No soiled fabrics added)                          1        1          Light sweet odor, very clean                                                  overall                                                   2        2          Light sweet odor, clean overall                           3        3          Best balance between treatments                                               1 & 6, some fatty, bleachy odor                           4        --         Not tested                                                5        4          Fatty bleachy odor                                        6        5          Strongest fatty bleach odor of                                                series                                                    Test #2                                                                       1        3          Clean, slight sweet note                                  2        5          Sour chemical, oily, alpha-chloro                                             odor                                                      3        2          Clean, slight chemical, oily odor                         4        1          Cleanest of series                                        5        --         Not tested                                                6        4          Fatty, bleach odor                                        Test #3                                                                       1        5          Poor overall, too much of dirty                                               alpha-chloro odor                                         2        --         Not tested                                                3        3          Alpha-chloro odors initially,                                                 but dissipated quickly                                    4        1          Very good overall, clean, no                                                  bleach odors                                              5        2          Good overall, some bleachy but                                                much more acceptable than #6                              6        4          Typical bleach odor, sour, fatty                          Test #4 (Special conditions: 95° F. (35° C.)                    1        4          Dirty alpha-chloro odors                                                      (i.e., sweet), strong soil odor                           2        --         Not tested                                                3        1          Clean, trace of alpha-chloro                                                  odor, good overall                                        4        2          Same as #3                                                5        5          Strong bleach and alpha-chloro                                                odors, poor overall                                       6        3          Bleachy odor, soil odors present,                                             typical                                                   ______________________________________                                         Treatment:                                                                    1  100% alphachloro NOBS                                                      2  80:20 alphachloro NOBS:NOBS                                                3  60:40 alphachloro NOBS:NOBS                                                4  40:60 alphachloro NOBS:NOBS                                                5  20:80 alphachloro NOBS:NOBS                                                6  100% NOBS                                                             

As demonstrated above, the mixtures consistently show better odorprofiles than 100% NOBS. Under soil conditions, they also show betterodor profiles than 100% alpha-chloro NOBS.

What is claimed is:
 1. A peroxygen bleach activator comprising a mixture of compounds of the general formula ##STR34## where R is a straight or branched chain alkyl or alkenyl containing from about 4 to about 14 carbon atoms, R¹ is H, --CH₃, --C₂ H₅ or --C₃ H₇, L is a leaving group the conjugate acid of which has a pKa of about 4 to about 30, and X¹ is H, Cl, OCH₃ or OC₂ H₅ such that the weight ratio of substituted compounds wherein X¹ =OCH₃ OC₂ H₅ or Cl to unsubstituted compounds wherein X¹ =H is from about 1:9 to about 9:1.
 2. A mixture according to claim 1 wherein X¹ in the substituted compound of the mixture is Cl.
 3. A mixture of compounds according to claim 1 wherein L is selected from the group consisting of: ##STR35## wherein R and R¹ are as defined in claim 1, X in the substituted compound is Cl, R² is an alkyl chain containing from about 1 to 8 carbon atoms, R³ is H or R², and Y is H or a solubilizing group.
 4. A mixture of compounds according to claim 3 wherein Y is selected from the group consisting of --SO₃ ⁻ M⁺, --COO⁻ M⁺, and mixtures thereof, wherein M is selected from the group consisting of sodium, potassium and mixtures thereof.
 5. A mixture of compounds according to claim 4 wherein L has the formula ##STR36## and M is sodium or potassium.
 6. A mixture according to claim 1 wherein the ratio of substituted compounds to unsubstituted compounds is from about 3:7 to about 7:3.
 7. A mixture according to claim 6 wherein the ratio of substituted compounds to unsubstituted compounds is from about 6:4 to about 4:6.
 8. A mixture according to claim 7 wherein the compounds comprising the mixture are selected from the group consisting of sodium 4-(2-chlorooctanonyloxy)benzene sulfonate; sodium 4-(2-chlorononanoyloxy)benzene sulfonate; sodium 4-(3,5,5,trimethyl-2-chlorohexanoyloxy)benzene sulfonate; sodium 2-(2-chlorononaoyloxy)benzene sulfonate; sodium 2-(2-chloroanoyloxy)benzene sulfonate; sodium 2-(2-chlorooctanoyloxy)benzoate; sodium 2-(2-chlorononanoyloxy)benzoate; sodium 4-(2-chlorononanoyl)benzoate; sodium 4-octanoyloxybenzenesulfonate; sodium 4-nonanoyloxybenzene sulfonate, sodium 4-decanoyloxybenzene sulfonate, tetraacetyl ethylendiamine, tetraacetyl methylenediamine, and tetraacetyl glycouril.
 9. A bleaching composition comprising:(a) a peroxygen bleach compound capable of yielding hydrogen peroxide in an aqueous solution; and (b) a bleach activator according to claim 1; wherein the ratio of (a):(b) is about 10:1 to about 1:10.
 10. A composition according to claim 9 wherein the ratio of (a):(b) is from about 3:1 to about 1:4.
 11. A composition according to claim 10 wherein the ratio of (a):(b) is from about 3:1 to about 1:2.
 12. A composition according to claim 9 wherein the peroxygen bleaching compound is selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and mixtures thereof.
 13. A composition according to claim 12 wherein the peroxygen bleaching compound is sodium perborate monohydrate.
 14. A bleaching composition comprising, by weight:(a) from about 1% to about 60% of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; (b) from about 1% to about 30% of a detergent surfactant; (c) from about 0.5% to about 40% of a bleach activator mixture according to claim
 2. 15. The composition of claim 14 further comprising from about 10% to about 60% of a detergency builder.
 16. A composition according to claim 15 wherein the bleach activator is comprised of compound selected from the group consisting of sodium 4-(2-chlorooctanonyloxy)benzene sulfonate; sodium 4-(2-chlorononanoyloxy)benzene sulfonate; sodium 4-(3,5,5,trimethyl-2-chlorohexanoyloxy)benzene sulfonate; sodium 2-(2-chlorononaoyloxy)benzene sulfonate; sodium 2-(2-chloro-anoyloxy)benzene sulfonate; sodium 2-(2-chlorooctanoyloxy)benzoate; sodium 2-(2-chlorononanoyloxy)benzoate; sodium 4-(2-chlorononanoyl)benzoate; sodium 4-octanoyloxybenzenesulfonate; sodium 4-nonanoyloxybenzene sulfonate; sodium 4-decanoyloxybenzene sulfonate, tetraacetyl ethylendiamine, tetraacetyl methylenediamine, and tetraacetyl glycouril. 